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NPRE 498 Energy Storage

Hydrogen Storage (I)

The key to an efficient energy storage


Why Hydrogen?

• High gravimetric energy density• Clean• Abundant, the most numerous element in

the universe! • Therefore affordable, once made


Why Hydrogen Storage?

• Mediocre volumetric energy density • Do we have a hydrogen mine? • Gaseous under most circumstances

What are the problems?


Typical H Storage Means

• High pressure• Cryogenic • Chemical Hydrides • Metal Hydrides • Physical Sorption


Basic H Storage Requirements

• H mass percentage (~ 6%-wt at least)• Volumetric density (~0.15 kg/liter at least) • Low cost • Ease of recharge or regeneration • Fast release, fast recharge• Environmentally sound


• 3000, 5000, 7000 psi, maybe up to 10000• Gravimetric density up to 3%-wt H• Volumetric density ~ 0.06 kg/liter• Cost high for bottles > 7000 psi• Environmentally sound• But how about safety? it’s like a bomb!• Relative ease of refueling though taking time• Composite construction with metal liner

High Pressure H Storage


64.9 kg composite usage in the 1st hybrid vessel vs. 76.0 kg in the baseline tank(FW alone)

• The end-user H2 storage system weight efficiency = 1.67 kWh/kg vs. 1.50 kWh/kg inthe system with the baseline tank

• The end-user H2 storage system cost efficiency:•$11/lb CF

• $6/lb CF

Baseline $23.45 Fully Integrated $21.91

Baseline $18.74 Fully Integrated $17.79

Fully Separate $21.75

Fully Separate $17.63

14

ConstructionHigh Pressure H Storage


Approach: Advanced Fiber Placement- Boeing• Advanced Fiber Placement: A CNC process that adds multiple strips

of composite material on demand.– Maximum weight efficiency - places material where needed

– Fiber steering allows greater design flexibility

– Process is scalable to hydrogen storage tanks

– Optimize plies on the dome sections with minimal limitation on fiber angle

– Reinforce dome without adding weight to cylinder

Tape PlacementRoller

Tape PlacementRoller

6


Strength• Tank preparation and validation test

Representative smallest polaropening that the AFP process

can currently makeThe localized reinforcement protected

the dome regions very well

• Static Burst Result: 23420 PSI > 22804 PSI, EN standard(New European Standard superseding EIHP)

• 64.9 kg composite usage in the 1st hybrid vessel vs. 76 kgin the baseline tank (FW alone)

11.1 kg (14.6%) Savings!10


Cryogenic H Storage• -252.87°C !• Very energy consuming to cool• Energy consuming to maintain• Gravimetric density up to 8~9% • Volumetric density ~ 0.08 kg/liter• Cost high• Environmentally sound and safe• Relative ease of refueling• Vacuum Dewar


Relevance: High density cryogenic hydrogen enablescompact, lightweight, and cost effective storage

Cost effective: Cryogenicvessels use 2-4x less carbonfiber, reducing costs sharply athigher capacity

Compact: 235 L system holds151 L fuel (10.3-10.7 kg H2)

Source: TIAX

Hydrogen annual merit review, LLNL, June 8, 2010, p. 3 Cryogenic H2 fill line

Gaseous H2extraction line


Relevance: Cryogenic pressure vesselscan exceed 2015 H2 storage targets and approach ultimate

ultimate

Gen 3, 10.4 kgH2

Gen 2, 10.4 kgH2

Hydrogen annual merit review, LLNL, June 8, 2010, p. 4


Approach: reduce/eliminate H2 venting losses by researchingvacuum stability, insulation, and para-ortho conversion

Determine para-ortho effect onpressurization and venting losses

Directly measure para-orthopopulations

Determine vessel heat transfermechanism (radiation vs. conduction)

Evaluate vacuum stability bymeasuring pressure vesseloutgassing

Test ultra thin insulation for improvedvessel volume performance

Improve vessel design based onexperimental results



Hydrogen has two nuclear spin states:para-H2 (stable at 20 K) and ortho-H2

para-H2 stable at 20 K

para-H2 converts toortho-H2 when heated

Normal H2(25% para, 75% ortho)

is stable at 300 K

ortho-H2

para-H2



Para-ortho conversion absorbs energy & increases dormancy(equivalent to a second evaporation)

ortho-H2

para-H2

ΔU=700kJ/kg

Vaporization ΔU=452 kJ/kg



Chemical Hydrides

• Examples: NH3, N2H4, B2H6, NaBH4…• Gravimetric density up to 20%-wt (LiBH4)• Volumetric density up to 0.2 kg/liter• Many are safe and sound, but not always• Cost high except NH3 and hydrocarbons• Regeneration has been problematic • Utilization is less straight forwards than H2.


Chemical Hydrides: Examples• Hydrocarbons: CH4, C2H6… (complicated reforming

H2, dirty byproducts)• NH3 (Ammonia) N2H4 (hydrazine) (toxic and … it stinks) • B2H6 (diborane) (highly toxic)• Borohydrides (LiBH4, NaBH4…) (relatively safe) • Alanates (NaAlH4…) (highly reactive)


Chemical Hydrides: Borohydrides

• LiBH4, very high H content, but not soluble • NaBH4, 12%-wt H dry• NaBH4, can be made to 30% H2O

solution• NaBH4, 6%-wt H in 35% H2O stabilized

with ammonium hydroxide• Safe, low toxicity • Still a challenge in regeneration


Observed H2 Capacity, weight %

IRMOF-177

bridged cat./IRMOF-8

Ca(BH4)2

LiBH4/MgH2

Li3AlH6/Mg(NH2)2

LiNH2/MgH2

LiMn(BH4)3 Mg(BH4)(AlH4)

Na2Zr(BH4)6

PANI

8

10

8

6

4

2

0

16

14

12

100 200 300 400

Temperature for observed H2 release (ºC)H2 sorption temperature (ºC)

00-100-200

metal hydrides

Mg(BH4)2(NH3)2

Mg(BH4)2

solid AB (NH3BH3)

chemical hydrides

CH Regen.Required

sorbents

?

PCN-12C aerogelcarbide-deri ved CB/CMOF-74

MD C-foambridged cat./AX21

AB/cat. AlH3

MD C-foam LiBH4/CA

2015 Ca(BH4)2/2LiBH4

Ti-MOF-16M-doped CAPANI

Li-AB Mg(BH4)2(NH3)2AB ionic liq. AlB4H11

M-B-N-H MgH2

LiMgN Li3AlH6/LiNH21,6 naphthyridine

liq. AB/cat. Mg-Li-B-N-H

NaAlH4

NaMn(BH4)4PANI

2009 Progress & Accomplishments

Status at 2009 AMR ReviewMaterial capacity

must exceedsystem targets

Ultimate


Observed H2 Capacity, weight %

Mg(BH4)(AlH4)

solid AB (NH3BH3)

MD C-foamCsC24 Ti-MOF-16 Na2Zr(BH4)6 PANI

AB ionic liq.

Bridged cat/AX21

Ti(AB)4

AB+AF(Me-Cell)Mg(BH4)2(NH3)2AlB4H11

Mg(BH4)2(NH3)2

BC8

sorbents

LiBH4/CAMPK/PI-6 MgH2

AB/AT/PS soln Ca(AB)2LiBH4/Mg2NiH4

2015 Liq AB:MeAB LiNH2/MgH2 Mg-Li-B-N-HNaAlH4

LiMn(BH4)3 NaMn(BH4)4

9

12

10

8

6

4

2

0

16

14

-200 100 200 300 400

Temperature for observed H2 release (ºC)H2 sorption temperature (ºC)

00-100

metal hydridesMg(BH4)2(NH3)2

DADB

chemical hydrides

AB/LiNH2 LiBH4/MgH2

M-B-N-HPCN-6 KAB LiMgN Li3AlH6/LiNH2

MOF-74 PANI

AB/Cat. AlH3 Ca(BH4)2

PCN-12 LiAB Ca(BH4)2/2LiBH4

AB/IL (20% bminCl) Mg(BH4)2

Li-AB

IRMOF-177 1,6 naphthyridineAC (AX-21) Li3AlH6/Mg(NH2)2

C aerogelcarbide-deri ved CBC8B/C bridged cat./IRMOF-8

CsC24 M-doped CAC123BF8 AC(AX-21)

Material capacitymust exceed

system targets

Ultimate

2010 Progress & AccomplishmentsOpen symbols denote new materials since 2009 AMR

hydrogen storage (i) - mragheb.com 498es energy storage systems...npre 498 energy storage basic h...

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